EP2484409B1 - Maske - Google Patents
Maske Download PDFInfo
- Publication number
- EP2484409B1 EP2484409B1 EP10820156.7A EP10820156A EP2484409B1 EP 2484409 B1 EP2484409 B1 EP 2484409B1 EP 10820156 A EP10820156 A EP 10820156A EP 2484409 B1 EP2484409 B1 EP 2484409B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fine particles
- mask
- virus inactivating
- viruses
- virus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B18/00—Breathing masks or helmets, e.g. affording protection against chemical agents or for use at high altitudes or incorporating a pump or compressor for reducing the inhalation effort
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B18/00—Breathing masks or helmets, e.g. affording protection against chemical agents or for use at high altitudes or incorporating a pump or compressor for reducing the inhalation effort
- A62B18/02—Masks
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B18/00—Breathing masks or helmets, e.g. affording protection against chemical agents or for use at high altitudes or incorporating a pump or compressor for reducing the inhalation effort
- A62B18/02—Masks
- A62B18/025—Halfmasks
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B23/00—Filters for breathing-protection purposes
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B7/00—Respiratory apparatus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D9/00—Composition of chemical substances for use in breathing apparatus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
Definitions
- the present invention relates to a mask, and particularly to a mask that can inactivate various viruses adhering thereto even in the presence of lipids and proteins regardless of whether or not the viruses have an envelope.
- Patent Literatures 1 and 2 propose masks having the effect of inactivating viruses (reducing the infectivity of the viruses or deactivating the viruses)
- Patent Literature 1 proposes a mask having the effect of inactivating bacteria and viruses . More specifically, iodine is adsorbed on anion exchange fibers prepared by bonding ion exchangeable functional groups such as amino groups to the fiber matrix, and a cloth containing the iodine-adsorbed fibers is used for the body of the mask.
- a cloth supporting a component extracted from Sasa veitchii and an inorganic porous material is used for the body of the mask to impart the effect of inactivating viruses to the mask.
- US2009130161 discloses an antimicrobial and chemical deactivating composition for use in a liquid medium or for incorporation into a coating, structural plastic materials, thin microporous membranes, textiles for masks and sponges.
- the composition includes macrosize or submicron particles of silver, platinum with silver and their salts with parabens, oxide, salicylate, acetate, citrate, benzoate and phosphate along with copper and zinc salts of the same.
- Patent Literature 1 shows that the mask has an effect on bacteria such as Escherichia coli, no examples are given for viruses. Therefore, it is not known whether or not the mask has the effect of inactivating viruses.
- Patent Literature 2 an antiviral test on the mask is shown.
- the virus used in the test is an RS (Respiratory Syncytial) virus having an envelope.
- Viruses can be classified into those having no envelope such as noroviruses and those having an envelope such as influenza viruses. Even though a drug can inactivate viruses having an envelope, this drug may not be effective for viruses having no envelope.
- no examples of the mask are described for viruses having no envelope. Therefore, it is not known whether or not the mask has the same effect on viruses having no envelope.
- a mask is an article used to cover the mouth and nose of the wearer, and lipids and proteins contained in bodily fluids such as saliva may adhere to the mask. Therefore, it is preferable that the mask can inactivate viruses even in an environment in which lipids and proteins are present. However, the mask in Patent Literature 2 is not tested in such an environment.
- the present invention provides a mask that can inactivate viruses adhering thereto even in the presence of lipids and proteins regardless of whether or not the viruses have an envelope.
- a first aspect of the present invention provides a mask that can inactivate a virus adhering thereto, the mask characterized by comprising: a mask body provided with a member used when the mask is worn; and virus inactivating fine particles having an ability to inactivate viruses and held by the mask body, the virus inactivating fine particles being particles of at least one selected from the group consisting of platinum(II) iodide, palladium(II) iodide, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate.
- a second aspect of the invention is the mask according to the first aspect, characterized in that the virus inactivating fine particles are fixed to the mask body at least through a silane monomer and/or a polymerization product of the silane monomer.
- a third aspect of the invention is the mask according to the first aspect, characterized in that the virus inactivating fine particles are held by the mask body through groups of other inorganic fine particles that are fixed to the mask body through chemical bonds with a silane monomer and/or a polymerization product of the silane monomer.
- a fourth aspect of the invention is the mask according to any of the first to third aspects, characterized in that the mask body includes a plurality of breathable filter members stacked in a thickness direction of the mask body, and the virus inactivating fine particles are held by at least one of the plurality of filter members constituting the mask body.
- a fifth aspect of the invention is the mask according to the fourth aspect, characterized in that the virus inactivating fine particles are held at least by a filter member that is located on the innermost side when the mask is worn.
- a sixth aspect of the invention is the mask according to the fourth or fifth aspect, characterized in that the virus inactivating fine particles are held at least by a filter member that is located on the outermost side when the mask is worn.
- a seventh aspect of the invention is the mask according to any of the first to sixth aspects, characterized in that an average diameter of the virus inactivating fine particles is 1 nm or larger and smaller than 500 nm.
- a mask that can easily inactivate various viruses such as viruses surrounded by a membrane referred to as an envelope containing a lipid and viruses having no envelope, and that can inactivate the viruses even in the presence of, in addition to the viruses, lipids and proteins resulting from, for example, the adhesion of droplets.
- the mask 100 of the first embodiment includes a mask body 10 having a substantially rectangular shape and rubber cords 2 (corresponding to members used when the mask is worn) that are sewed onto both ends of the lengthwise edges of the mask body 10 and are to be stretched around ears.
- the mask body 10 includes a plurality of (three in the first embodiment) breathable filter members 1, and the filter members 1 are stacked in the thickness direction of the mask body 10 and integrated by welding.
- several (four in the first embodiment) pleats 4 extending in the lengthwise direction are formed in the mask body 10 so that the mask body can freely change its width according to the size of the faceof the wearer.
- the pleats 4 can open in a vertical direction, so that three-dimensional spaces are formed in front of the nose and mouth. Therefore, the contact of the mask with the mouth and nose is loosened. This facilitates respiration and reduces the amount of cosmetics adhering to the mask.
- integrating processing is not limited to the welder bonding, and any other method such as sewing may be used.
- Fig. 2 for the purpose of facilitating understanding, the pleats 4 and a band-shaped wire 3 described later are omitted from the figure.
- Fig. 2 for the purpose of facilitating the understanding of the present application, the plurality of filter members 1 are shown. However, this is only an example, and the filter member 1 may be composed of a single layer.
- the band-shaped wire 3 made of a bendable metal or resin is inserted into the upper edge of the mask body 10.
- the formation of a gap between the mask 100 of the first embodiment and the nose of the wearer can be prevented by bending the band-shaped wire 3 so as to extend along the shape of the nose of the wearer. Therefore, problems such as fogging of eyeglasses by breath and intrusion of viruses together with external air through the gap can be resolved.
- the filter member 1 constituting the mask body 10.
- the three filter members 1 are stacked in the thickness direction of the mask body 10.
- Virus inactivating fine particles having a virus inactivating ability are bonded, at least through a silane monomer or an oligomer obtained by polymerization of the silane monomer, to the outer surfaces of the filter members 1 that are located on the outermost and innermost sides in the thickness direction, i.e., are located on the outermost and innermost sides during wearing of the mask.
- No particular limitation is imposed on the dimensions of the filter member 1, and a person skilled in the art can appropriately set the dimensions. For example, the dimensions of the filter member 1 for adults may be different from those for kids.
- the filter member 1 is composed of a single layer, the virus inactivating fine particles are bonded to both sides of the filter member 1.
- the virus inactivating fine particles are fine particles of at least one inorganic compound selected from the group consisting of platinum(II) iodide, palladium(II) iodide, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate and can inactivate viruses regardless of whether or not the viruses have an envelope.
- the mask 100 of the first embodiment can be considered to hold an antiviral agent including fine particles of at least one inorganic compound selected from the group consisting of platinum(II) iodide, palladium(II) iodide, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate.
- the virus inactivating fine particles according to the first embodiment can inactivate viruses even in the presence of proteins and lipids.
- the virus inactivating mechanism of the virus inactivating fine particles is not clear.
- the mechanism is assumed to be as follows. When the virus inactivating fine particles come into contact with moisture in air or droplets, part of the virus inactivating fine particles undergoes an oxidation-reduction reaction. This causes some effect on the surface electric charge or membrane protein or DNA of the viruses adhering to the mask 100 of the first embodiment, and the viruses are thereby inactivated.
- the average particle diameter is preferably 1 nm or larger and smaller than 500 nm.
- the average particle diameter is smaller than 1 nm, the virus inactivating fine particles are physically unstable and agglutinate with each other. Therefore, it is difficult to fix the particles on the filter member 1 uniformly.
- the average particle diameter is 500 nm or larger, the adhesion between the particles and the filter member 1 is lower than that when the average particle diameter falls within the above range.
- the average particle diameter is a volume average particle diameter.
- the virus inactivating fine particles are fixed to the filter member 1 through a binder.
- the binder used No particular limitation is imposed on the binder used.
- the molecular weights of the silane monomer and oligomer obtained by polymerization of the silane monomer are low. Therefore, these monomer and oligomer are preferred because the contact between the virus inactivating fine particles and viruses is less likely to be prevented, and the viruses can be effectively inactivated.
- the adhesion of the binder to the filter member 1 used as substrates is improved by using the silane monomer and/or the oligomaer as the binder, the virus inactivating fine particles can be more stably supported on the filter member 1.
- silane monomers used for the mask 100 of the first embodiment include silane monomers represented by a general formula X-Si(OR) n (n is an integer of from 1 to 3).
- X is a functional group that reacts with an organic material, and examples thereof include a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryloxy group, an isocyanate group, a polysulfide group, an amino group, a mercapto group, and a chloro group.
- Each OR is a hydrolyzable alkoxy group such as a methoxy group or an ethoxy group, and the three functional groups in the silane monomer may be the same or different.
- alkoxy groups including methoxy and ethoxy groups are hydrolyzed to form silanol groups.
- the reactivity of such a silanol group, a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryloxy group, an isocyanate group, and functional groups having an unsaturated bond and the like is known to be high. More specifically, in the mask 100 of the first embodiment, the virus inactivating fine particles are firmly held on the surface of the filter member 1 by the chemical bonds through the silane monomer having high reactivity.
- silane monomer represented by the above general formula examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane, a hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropy
- silane-based oligomers examples include commercially available oligomers KC-89S, KR-500, x-40-9225, KR-217, KR-9218, KR-213, and KR-510, which are all products of Shin-Etsu Chemical Co., Ltd. These silane-based oligomers may be used alone, as a mixture of two or more thereof, or as a mixture with one or two or more of the above-described silane monomers.
- the use of the silane monomer or oligomer thereof as a binder allows the exposed areas of the fixed virus inactivating fine particles to be increased. Therefore, the probability of contact of viruses adhering to the surface of the mask 100 with the virus inactivating fine particles can be higher than that when the virus inactivating fine particles are fixed to the filter member 1 using a binder such as a synthetic resin other than the silane monomer and oligomer thereof. The viruses can thereby be effectively inactivated even by using a small amount of the virus inactivating fine particles.
- the mask 100 of the present embodiment can maintain its virus inactivating effect for a longer time.
- the virus inactivating fine particles may be held by a condensation reaction, amide bonds, hydrogen bonds, ion bonds, van der Waals forces, or physical adsorption. This can be achieved by selecting an appropriate silane monomer to be used.
- the form of holding the virus inactivating fine particles on the filter member may be appropriately selected by a person skilled in the art.
- the respective fine particles may be scattered on the filter member 1.
- the inorganic fine particles may be held as inorganic fine particle aggregates arranged two- or three-dimensionally. More specifically, the virus inactivating fine particles may be held, for example, in a dot, island, or thin-film form.
- virus inactivating fine particles When the virus inactivating fine particles are held as three-dimensional aggregates, they include particles bonded to the filter member 1 through the silane monomer or oligomer thereof (such particles are referred to as virus inactivating fine particles a) and particles bonded to the filter member 1 through at least the virus inactivating fine particles a.
- the virus inactivating fine particles are held on the filter member 1 as three-dimensional aggregates because a large number of fine irregularities are formed on the surface of the filter member 1 and the adhesion of dust and the like to the mask body 10 is suppressed by the irregularities.
- the suppression of the adhesion of dust and the like allows the virus inactivating effect of the mask 100 to be maintained for a longer time.
- a functional material optionally used, in addition to the virus inactivating fine particles, to impart a desired function to the mask 100 may be held on the surfaces of the filter member 1 constituting the mask body 10.
- the functional material include other antiviral agents, antimicrobial agents, antifungal agents, anti-allergen agents, and catalysts.
- Such a functional material may be fixed to the filter member 1, the virus inactivating fine particles, and the like through, for example, a binder.
- the functional material may be bonded to the filter member 1 through chemical bonds between the silane monomer or oligomer bonded to the surface of the functional material and the surface of the filter.
- the amount of the virus inactivating fine particles held by the mask body 10 is preferably 1.0 percent by mass to 80.0 percent by mass to the sum total of mass of the substances held on the filter member 1 constituting the mask body 10 and more preferably 5.0 percent by mass to 60.0 percent by mass.
- the amount of the virus inactivating fine particles is less than 1.0 percent by mass, the virus inactivating activity is lower than that when the amount falls within the above range.
- the amount is larger than 80.0 percent by mass, the virus inactivating effect is not largely different from that when the amount falls within the above range.
- the substances held on the filter member 1 can include a silane monomer or oligomer thereof.
- the filter member 1 holding the virus inactivating fine particles may be held on surfaces with various forms.
- the filter member 1 include fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics, and mixed-paper sheets that are formed of materials, for example, various resins, synthetic fibers, natural fibers such as cotton, hemp, and silk, and Japanese paper obtained from natural fibers, that can be chemically bonded to the silane monomer on the virus inactivating fine particles at the surface of the filter member 1.
- Such materials of the filter member 1 include polyester, polypropylene, polyethylene terephthalate, nylon, acrylic, polyacrylic acid, polymethyl methacrylate, rayon, acetate, triacetate, cotton, hemp, wool, silk, and bamboo.
- a person skilled in the art can appropriately set the shape of the filter member 1 according to the shape of the mask body 10.
- the manufacture method of the mask 100 of the first embodiment that has the virus inactivating fine particles held thereon will next be described more specifically.
- At least one is selected from platinum(II) iodide, palladium(II) iodide, copper(I) iodide, silver(I) iodide, and copper (I) thiocyanate, and the selected material is pulverized into particles of the order of sub-micrometers to micrometers using, for example, a jet mill, a hammer mill, a ball mill, or a vibration mill to obtain virus inactivating fine particles. No particular limitation is imposed on the pulverization, and any of wet and dry processes can be used.
- the pulverized virus inactivating fine particles are dispersed in a solvent such as water, methanol, ethanol, MEK, acetone, xylene, or toluene.
- a solvent such as water, methanol, ethanol, MEK, acetone, xylene, or toluene.
- other materials such as a binder component including a silane monomer or an oligomer thereof and functional materials may be mixed with the dispersion.
- a dispersing agent such as a surfactant is added if necessary, and the resultant mixture is dispersed and pulverized using an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a homogenizer, thereby preparing a slurry containing the virus inactivating fine particles dispersed therein.
- the particle diameter of the virus inactivating fine particles is reduced, and these particles are arranged on the surface of the filter member 1 constituting the mask body 10 without excessively large gaps formed between the particles.
- the particle density of the virus inactivating fine particles can thereby be increased, and accordingly, a high virus inactivating ability can be achieved.
- the slurry prepared as described above is applied to the surface of the filter member 1 using a method such as a dipping method, a spraying method, a roll coating method, a bar coating method, a spin coating method, a gravure printing method, an offset printing method, a screen printing method, or an inkjet printing method. If necessary, the solvent is removed by, for example, heating and drying.
- the functional groups on the surface of the filter member 1 are chemically bonded to the silane monomer through graft polymerization by re-heating or graft polymerization by irradiation with infrared rays, ultraviolet rays, an electron beam, or radioactive rays such as ⁇ rays.
- the virus inactivating fine particles are bonded to each other through the silane monomer.
- a mask body 10 is formed using the filter member 1.
- the formed mask body 10 is pleated, and rubber cords 2 are sewed to obtain the mask 100 of the first embodiment.
- the three filter members 1 are stacked and sewed to each other, and an integrated stacked body is thereby obtained and used as the mask body 10.
- viruses can be inactivated regardless of the types of genomes and whether or not the viruses have an envelope.
- the viruses include rhinoviruses, polioviruses, foot and mouth disease viruses, rotaviruses, noroviruses, enteroviruses, hepatoviruses, astroviruses, sapoviruses, hepatitis E viruses, type A, B, and C influenza viruses, parainfluenza viruses, mumps viruses, measles viruses, human metapneumoviruses , RS viruses, Nipah viruses, Hendra viruses, yellow fever viruses, dengue viruses, Japanese encephalitis viruses, West Nile viruses, hepatitis B and C viruses, eastern and western equine encephalitis viruses, O'nyong-nyong viruses, rubella viruses, Lassa viruses, Junin viruses, Machupo viruses, Guanarito viruses, Sabia viruses, Crimean-Congo hemorrhagic
- viruses can be inactivated even in the presence of, in addition to the viruses, lipids and proteins resulting from, for example, the adhesion droplets.
- the viruses adhering to the mask can be inactivated. Therefore, the wearer can be prevented from viral infection, and the spread of viruses from an infected person can be suppressed. In addition, the occurrence of secondary infection due to contact with a used mask 100 can be reduced.
- second inorganic fine particles used as additional fine particles are held on the filter members 1.
- the second inorganic fine particles together with the first inorganic fine particles form inorganic fine particle aggregates in which the inorganic fine particles are arranged two- or three-dimensionally.
- the inorganic particle aggregates containing the first inorganic fine particles and the second inorganic fine particles are held on the filter members 1. Structures common to those in the first embodiment are denoted by the same reference numerals, and the description will be omitted.
- the second inorganic fine particles are bonded to the filter member 1 through a silane monomer or oligomer thereof and also are bonded to each other through the silane monomer or oligomer thereof. Therefore, in the second embodiment, the first inorganic fine particles serving as virus inactivating fine particles are bonded to the filter member 1 and the second inorganic fine particles through the silane monomer or oligomer thereof and are held on the filter member 1. In the second embodiment, the first inorganic fine particles are held on the filter member 1 so as to be entangled with groups of the second inorganic fine particles bonded to each other through the silane monomer or oligomer thereof. Therefore, the first inorganic fine particles are prevented from falling off the filter member 1 not only by the chemical bonds but also physically. In the mask of the second embodiment, the virus inactivating fine particles are more effectively prevented from falling off as compared to those in the mask of the first embodiment. Therefore, the virus inactivating ability can be maintained for a longer time.
- the groups of the second inorganic fine particles that are bonded to each other through the silane monomer prevent the first inorganic fine particles from falling off the filter member 1. Therefore, the first inorganic fine particles may not form bonds with the second inorganic fine particles and the filter member through the silane monomer.
- the first inorganic fine particles serving as the virus inactivating fine particles are bonded to the second inorganic fine particles and the filter member through the silane monomer and oligomer thereof, and accordingly, the surfaces of the first inorganic fine particles are exposed, as in the first embodiment. Therefore, the probability of contact of viruses adhering to the surface of the mask 100 with the virus inactivating fine particles can be made higher than that when the virus inactivating fine particles are fixed to the filter member 1 using, for example, a general binder, so that the viruses can be effectively inactivated even by using a small amount of the virus inactivating fine particles.
- the second inorganic fine particles according to the second embodiment are bonded to the silane monomer or oligomer thereof, and a person skilled in the art can select appropriate second inorganic fine particles.
- nonmetal oxides, metal oxides, metal composite oxides, nitrides, carbides, silicates, and mixtures thereof can be used.
- the second inorganic fine particles may be amorphous or crystalline. Examples of the nonmetal oxides include silicon oxide.
- metal oxides examples include magnesium oxide, barium oxide, barium peroxide, aluminum oxide, tin oxide, titanium oxide, zinc oxide, titanium peroxide, zirconium oxide, iron oxide, iron hydroxide, tungsten oxide, bismuth oxide, indium oxide, gibbsite, boehmite, diaspore, antimony oxide, cobalt oxide, niobium oxide, manganese oxide, nickel oxide, cerium oxide, yttrium oxide, and praseodymium oxide.
- metal composite oxides examples include barium titanium oxide, cobalt aluminum oxide, zirconium lead oxide, niobium lead oxide, TiO 2 -WO 3 , AlO 3 -SiO 2 , WO 3 -ZrO 2 , WO 3 -SnO 2 , CeO 2 -ZrO 2 , In-Sn, Sb-Sn, Sb-Zn, In-Sn-Zn, B 2 O 3 -SiO 2 , P 2 O 5 -SiO 2 , TiO 2 -SiO 2 , ZrO 2 -SiO 2 , Al 2 O 3 -TiO 2 , Al 2 O 3 -ZrO 2 , Al 2 O 3 -CaO, Al 2 O 3 -B 2 O 3 , Al 2 O 3 -P 2 O 5 , Al 2 O 3 -CeO 2 , Al 2 O 3 -Fe 2 O 3 , TiO 2 -ZrO 2 , TiO 2
- Examples of the nitrides include titanium nitride, tantalum nitride, and niobium nitride.
- Examples of the carbides include silicon carbide, titanium carbide, and niobium carbide.
- Examples of the adsorptive silicates include: synthetic zeolites such as zeolite A, zeolite P, zeolite X, and zeolite Y; natural zeolites such as clinoptilolite, sepiolite, and mordenite; layer silicate compounds such as kaolinite, montmorillonite, Japanese acid clay, and diatomaceous earth; and cyclosilicate compounds such as wollastonite and neptunite.
- Other examples include phosphate compounds such as tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, and hydroxyapatite, activated carbon, and porous glass.
- particles having the ability to adsorb proteins when used as the second inorganic fine particles, they can adsorb allergen proteins such as pollen and mites. Therefore, the combined use of such particles with the above-described virus inactivating fine particles having the effect of denaturing proteins can provide a mask having not only the virus inactivating ability but also anti-allergen performance.
- the diameter of the second inorganic fine particles is preferably 500 nm or smaller and more preferably 300 nm or smaller.
- the diameter is preferably 1 nm or larger.
- At least one is selected from platinum (II) iodide, palladium(II) iodide, copper(I) iodide, silver(I) iodide, and copper(I) thiocyanate, and the selected material is pulverized into particles of the order of micrometers using, for example, a jet mill, a hammer mill, a ball mill, or a vibration mill to obtain virus inactivating fine particles. No particular limitation is imposed on the pulverization, and any of wet and dry processes can be used.
- the pulverized virus inactivating fine particles are mixed with the second inorganic fine particles to which the silane monomer has been bonded through dehydration condensation, and the mixture is dispersed in a solvent such as water, methanol, ethanol, MEK, acetone, xylene, or toluene.
- a solvent such as water, methanol, ethanol, MEK, acetone, xylene, or toluene.
- other materials such as a binder component and functional materials may be added to the solvent at this point.
- a dispersing agent such as a surfactant is added if necessary, and the resultant mixture is dispersed and pulverized using an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a homogenizer to prepare a slurry containing the virus inactivating fine particles and the second inorganic fine particles dispersed therein.
- an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a homogenizer to prepare a slurry containing the virus inactivating fine particles and the second inorganic fine particles dispersed therein.
- the particle density of the virus inactivating fine particles can thereby be increased, and the groups of the second inorganic fine particles can be more firmly fixed to the surface of the filter member 1 constituting the mask body 10. Therefore, a high virus inactivating ability can be achieved, and the virus inactivating ability can be maintained for a longer time.
- the chemical bonds between the second inorganic fine particles and the silane monomer can be formed by an ordinary method.
- the silane monomer is added to a dispersion, and the resultant dispersion is heated under reflux to allow the silane monomer to be bonded to the surfaces of the second inorganic fine particles through a dehydration-condensation reaction to thereby form thin films made of the silane monomer.
- the silane monomer is added to a dispersion that has been subjected to pulverization to reduce the size of the particles, or alternatively, the silane monomer is added to a dispersion of the second inorganic fine particles, and the resultant dispersion is subjected to pulverization to reduce the size of the particles.
- the solid and liquid are separated from each other, and the separated solid is heated at 100°C to 180°C to allow the silane monomer to be bonded to the surfaces of the second inorganic fine particles through a dehydration-condensation reaction.
- the resultant particles are pulverized and then re-dispersed.
- the amount of the silane monomer to be added to the dispersion depends on the average particle diameter and material of the second inorganic fine particles .
- the amount is 3 percent by mass to 30 percent by mass based on the mass of the second inorganic fine particles
- the mutual bonding strength between the second inorganic fine particles and the bonding strength between the groups of the second inorganic fine particles and the filter member constituting the mask body 10 of the present invention do not cause any practical problems .
- Even after the silane monomer and the like are bonded to the first inorganic fine particles the surfaces of the first inorganic fine particles are exposed sufficiently.
- an excess of silane monomer that is not involved in the bonding may be present.
- the above-prepared slurry is applied to the surface of the filter member 1 using a method such as a dipping method, a spraying method, a roll coating method, a bar coating method, a spin coating method, a gravure printing method, an offset printing method, a screen printing method, or an inkjet printing method. If necessary, the solvent is removed by heating and drying and the like.
- the functional groups on the surface of the filter member 1 are chemically bonded, through graft polymerization by re-heating or graft polymerization by irradiation with infrared rays, ultraviolet rays, an electron beam, or radioactive rays such as ⁇ rays, to the silane monomer bonded to the surfaces of the second inorganic fine particles which face the surface of the filter member 1.
- the silane monomers on the surfaces of the second inorganic fine particles are chemically bonded to each other to form an oligomer.
- the virus inactivating fine particles are bonded to the second inorganic fine particles through the silane monomer.
- the virus inactivating fine particles are bonded to the second inorganic fine particles and the mask body 10 through the silane monomer and formed oligomer.
- the virus inactivating fine particles having a virus inactivating ability are surrounded by the groups of the second inorganic fine particles, and the filter member 1 holding the virus inactivating fine particles on the surface thereof is thereby obtained.
- the mask body 10 is formed using the filter members 1, and the mask body 10 is pleated. Then rubber cords 2 are sewed onto the mask body 10 to obtain the mask 100 of the first embodiment.
- the mask body 10 is formed using the filter members 1, and the mask body 10 is pleated.
- rubber cords 2 are sewed onto the mask body 10 to obtain the mask 100 of the first embodiment.
- three filter members 1 are stacked and sewed to each other, and an integrated stacked body is thereby obtained and used as the mask body 10.
- the silane monomer is bonded to the second inorganic fine particles in advance, but this mode is not a limitation.
- the virus inactivating fine particles, second inorganic fine particles to which no silane monomer has been bonded, and the silane monomer may be dispersed in a dispersion medium.
- a person skilled in the art may appropriately set the amount of the silane monomer added. As in the above description, the amount added may be, for example, 3 percent by mass to 30 percent by mass based on the mass of the second inorganic fine particles.
- the mutual bonding strength between the second inorganic fine particles and the bonding strength between the groups of the second inorganic fine particles and the filter member constituting the mask body 10 of the present invention do not cause any practical problems. Even after the silane monomer is bonded to the second inorganic fine particles, the surfaces of the first inorganic fine particles are exposed sufficiently.
- the present invention is not limited thereto, and other embodiments are, of course, possible.
- the shape of the mask 100 is not limited to the type shown in Fig. 1 .
- the mask may have a shape obtained by stamping using a hot press.
- the invention can be applied to a gauze mask shown in Fig. 4 .
- the filter members 1 stacked may have different functions.
- filter members 1 that are to be located on the outermost and innermost sides during wearing of the mask may be subjected to antibacterial and deodorizing treatment to prevent bad odors and the propagation of bacteria.
- the mask body is composed of a plurality of filter members 1.
- the mask body can be composed of one filter member 1.
- viruses can be more efficiently inactivated as compared to when one filter member 1 is used to form a mask body.
- a filter member having a function or configuration different from those of the above-described filter members 1 having the virus inactivating fine particles held thereon may be stacked on these filter members 1 to constitute a mask body 10.
- the filter members 1 having the virus inactivating fine particles held thereon are disposed on the outermost and innermost sides when the mask is worn, and a filter member, such as an electret, having high dust collecting efficiency (hereinafter may be referred to as an electret filter member) is disposed between these filter members 1.
- this mask body 100 is configured such that the electret filter member and the filter members 1 are stacked so as to be sandwiched between the two filter members 1, and the virus inactivating fine particles are held at least on the filter members disposed on the outermost and innermost sides when the mask is worn.
- the filter members 1 are stacked on the electret filter member so as to be located on the outermost and innermost sides.
- viruses in droplets sprayed from carriers of the viruses and viruses floating in the air can be collected and inactivated by the outermost filter member 1, and viruses present in droplets from the mouth and nose of the wearer can be collected and inactivated by the innermost filter member 1 facing the mouth and nose.
- the filter member 1 having the inorganic particles held thereon is disposed on the innermost side when the mask is worn.
- viruses present in droplets from the mouth and nose of the wearer can be inactivated, and the virus inactivating effect can be improved by moisture contained in the breath of the wearer.
- the inactivating effect is significantly reduced by lipids and proteins originating from the wearer, when a filter member having such a material held thereon is disposed on the innermost side.
- the virus inactivating fine particles held thereon can maintain its inactivating ability even in the presence of lipids and proteins
- the filter member holding the virus inactivating fine particles is disposed at least on the innermost side, the virus inactivating effect can be enhanced.
- the filter member disposed on the outermost side when the mask is worn may hold the virus inactivating fine particles thereon.
- viruses in droplets sprayed from carriers of the viruses and viruses floating in the air can be inactivated on the outermost side. Therefore, even if a hand comes into contact with the surface of the mask when the mask is worn or removed, secondary infection is less likely to occur.
- the filter members holding the virus inactivating fine particles are disposed at least on the outermost and innermost sides when the mask is worn, because the virus inactivating effect can be improved and also viruses in droplets and viruses floating in the air can be inactivated.
- the virus inactivating fine particles are held on the outer surfaces of the filter members through the silane monomer or oligomer thereof .
- the virus inactivating fine particles may be held on the mask body in a different manner.
- the virus inactivating fine particles may be held on the filter member 1 through a binder component. No particular limitation is imposed on the binder component so long as it has high adhesion to the base material (the material of the filter members 1).
- the usable material examples include synthetic resins such as polyester resins, amino resins, epoxy resins, polyurethane resins, acrylic resins, water-soluble resins, vinyl-based resins, fluoro resins, silicone resins, cellulosic resins, phenolic resins, xylene resins, and toluene resins; and natural resins such as castor oil and drying oils for example, linseed oil and tung oil.
- synthetic resins such as polyester resins, amino resins, epoxy resins, polyurethane resins, acrylic resins, water-soluble resins, vinyl-based resins, fluoro resins, silicone resins, cellulosic resins, phenolic resins, xylene resins, and toluene resins
- natural resins such as castor oil and drying oils for example, linseed oil and tung oil.
- the virus inactivating fine particles are held on the surfaces of the filter members, but this is not a limitation.
- the virus inactivating fine particles maybe held in the mask as awhole.
- the virus inactivating fine particles may be held so as to be surrounded by the fibers constituting the filter members 1.
- the virus inactivating ability of the virus inactivating fine particles formed of any of platinum (II) iodide, palladium (II) iodide, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate and to be held on the filter member 1 of the mask body 10 was examined.
- the examination was performed using a hemagglutination (HA) inhibition assay generally used to measure the titer of a virus.
- HA hemagglutination
- An influenza virus influenza A/Kitakyusyu/159/93(H3N2) cultured in MDCK cells was used as a subject virus.
- a two-fold dilution series of a virus solution was prepared in a plastic-made 96 well plate. Then 50 ⁇ L of a 0.5% chicken blood cell suspension was added to each of the wells. The wells were allowed to stand at 4°C for 1 hour, and then an HA titer was determined. The determined HA titer was 128. Next, virus inactivating fine particles was diluted to 10 percent by mass with phosphate buffered saline. 450 ⁇ L of the virus solution was added to 450 ⁇ L of the diluted solution, and the resultant solution was allowed to react at room temperature for 10 minutes under stirring using a micro-tube rotator.
- the powder was precipitated by centrifugation, and 150 ⁇ L of the supernatant was collected and used as a sample. A two-fold dilution series of the obtained sample solution was prepared. Then an equal amount of a 0.5% chicken blood cell suspension was added. The resultant solutions were allowed to stand at 4°C for 60 minutes, and an HA titer was determined. The results are shown in Table 1.
- the virus inactivating fine particles formed of any of platinum (II) iodide, palladium (II) iodide, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate were found to have the ability to inactivate the influenza virus with an HA titer of 2 to 64.
- a commercially available powder of copper (I) iodide (product of Wako Pure Chemical Industries, Ltd., Wako 1st grade) was used as virus inactivating fine particles having a virus inactivating ability and was pulverized into an average particle diameter of 170 nm using a dry pulverizer, Nano Jetmizer (product of Aishin Nano Technologies CO. , Ltd.).
- the pulverized copper (I) iodide fine particles were added to ethanol in an amount of 2. 0 percent by mass, and tetramethoxy silane (KBM-04, product of Shin-Etsu Chemical Co. , Ltd.) was further added in an amount of 0.4 percent by mass.
- the mixture was pre-dispersed using ahomogenizer for 5 minutes to prepare a slurry.
- the average particle diameter as used herein is a volume average particle diameter.
- a rayon nonwoven fabric product of SHINWA Corp.
- 20 g/m 2 was immersed in the prepared slurry. Any excess of the slurry was removed, and the nonwoven fabric was dried at 120°C for 10 minutes to obtain a filter member 1 having a virus inactivating effect.
- methacryloxypropyltrimethoxy silane (KBM-503, product of Shin-Etsu Chemical Co., Ltd.), a silane monomer having an unsaturated bonding part, was subjected to dehydration-condensation by an ordinary method to covalently-bond the silane to the surfaces of zirconium oxide particles (PCS, product of Nippon Denko Co., Ltd.), and the resultant particles were used as second inorganic fine particles.
- 100.0 g of the second inorganic fine particles were pre-dispersed in ethanol and were pulverized and dispersed using a bead mill to obtain a slurry having an average particle diameter of 15.1 nm.
- the average particle diameter as used herein is a volume average particle diameter.
- the above two types of slurries were mixed in a mixing ratio of 40 percent by mass of the copper thiocyanate dispersion and 60 percent by mass of the zirconium oxide particle dispersion, and ethanol was added to the mixture such that the concentration of the solid content was adjusted to 3 percent by mass (hereinafter the resultant slurry is referred to as a mixed slurry).
- tetramethoxy silane KBM-04, product of Shin-Etsu Chemical Co., Ltd.
- a rayon nonwoven fabric product of KURARAYKURAFLEX Co., Ltd.
- tetramethoxy silane (KBM-04, product of Shin-Etsu Chemical Co., Ltd.) was added to the above slurry in an amount of 0.3 percent by mass, and the particles were dispersed using a homogenizer.
- a rayon nonwoven fabric product of KURARAYKURAFLEX Co., Ltd.
- a rayon nonwoven fabric product of KURARAYKURAFLEX Co., Ltd.
- a commercially available powder of silver (I) iodide (product of Wako Pure Chemical Industries, Ltd., chemical use) was used as virus inactivating fine particles (first inorganic fine particles) having a virus inactivating ability.
- Methacryloxypropyltrimethoxy silane KBM-503, product of Shin-Etsu Chemical Co., Ltd.
- a silane monomer having an unsaturated bonding part was subjected to dehydration-condensation by an ordinary method to covalently-bond the silane to the surfaces of zirconium oxide particles (product of Nippon Denko Co., Ltd.), and the resultant particles were used as second inorganic fine particles .
- tetramethoxy silane was added to the slurry in an amount of 0.3 percent by mass, and a rayon nonwoven fabric (product of KURARAYKURAFLEX Co., Ltd.) of 18 g/m 2 was dipped with the resultant slurry and dried to obtain a filter member 1 having a virus inactivating effect.
- a rayon nonwoven fabric product of KURARAYKURAFLEX Co., Ltd.
- a commercially available powder of copper (I) iodide (product of Wako Pure Chemical Industries, Ltd., Wako 1st grade) was used as virus inactivating fine particles (first inorganic fine particles).
- Methacryloxypropyltrimethoxy silane KBM-503, product of Shin-Etsu Chemical Co., Ltd.
- a silane monomer having an unsaturated bonding part was subjected to dehydration-condensation by an ordinary method to covalently-bond the silane to the surfaces of zirconium oxide particles (PCS, product of Nippon Denko Co., Ltd.), and the resultant particles were used as second inorganic fine particles .
- a rayon nonwoven fabric product of KURARAYKURAFLEX Co., Ltd.
- 18 g/m 2 was dipped with the resultant slurry and dried to obtain a filter member 1 having a virus inactivating effect.
- a filter member 1 having a virus inactivating effect was obtained under the same conditions as in Example 5 except that tetramethoxy silane (KBM-04, product of Shin-Etsu Chemical Co., Ltd.) was added in an amount of 0.3 percent by mass to the slurry used in Example 5.
- tetramethoxy silane KBM-04, product of Shin-Etsu Chemical Co., Ltd.
- a filter member of Comparative Example 1 was obtained under the same conditions as in Example 6 except that the virus inactivating fine particles used in Example 6 were not added.
- influenza viruses A/yamagata/1/08(H1N1), A/kitakyushu/159/93(H3N2), and B/Bangkok/163/90 were used as subject viruses.
- a sample nonwoven fabric sheet (5 cm x 5 cm) of one of Examples 1, 3, 5, and 6 and Comparative Examples 1 and 2 was placed on three untreated nonwoven fabric sheets, and the sheets were held with tweezers.
- AAN shutto atomizer product of Keytron, an apparatus that can spray liquid as droplets having a size corresponding to the size of oral-nasal droplets
- the sample sprayed with the virus solution was placed in a sterilized plastic petri dish. After sensitization for 60 minutes, 1 mL of a bouillon solution was added to wash the virus off.
- reaction sample was diluted with an MEMdiluting solution until 10 -2 to 10 -5 (ten-fold serial dilution), and 100 ⁇ L of the diluted sample solutions were inoculated on MDCK cells.
- a 0.7% agar medium was placed thereon, and the virus was cultured at 34°C in 5% of CO 2 for 48 hours in an incubator.
- formalin-fixation and methylene blue staining were performed, the number of plaques formed was counted to compute the infectivity titer of the virus (PFU/0.1 mL, Log10) (PFU: plaque-forming units), and the computed infectivity titer of the virus was compared with that of a control.
- BSA bovine serum albumin
- AAN shut to atomizer product of Keytron, an apparatus that can spray liquid as droplets having a size corresponding to the size of oral-nasal droplets
- the sample sprayed with the virus solution was placed in a sterilized plastic petri dish. After sensitization for 60 minutes, 1 mL of a bouillon solution was added to wash the virus off.
- reaction sample was diluted with an MEM diluting solution until 10 -2 to 10 -5 (ten-fold serial dilution), and 100 ⁇ L of the diluted sample solutions were inoculated onMDCK cells .
- virus adsorption for 90minutes a 0.7% agar medium was placed thereon, and the virus was cultured at 34°C in 5% of CO 2 for 48 hours in an incubator. After formalin-fixation and methylene blue staining were performed, the number of plaques formed was counted to compute the infectivity titer of the virus (PFU/0.1 mL, Log10) (PFU: plaque-forming units), and the computed infectivity titer was compared with that of a control.
- Example 1 the inactivating effect on the A type and B type influenza viruses was found in Examples 1, 3, 5, and 6. Particularly, in Examples 1, 3, and 5, the effect observed was very high, i.e., the inactivation ratio after 60 minutes was 99.9999% or higher. In Example 6, a small amount of the H3N2 virus remained non-inactivated. However, the inactivation ratio was very high (99.9996%). Even in the presence of the protein, similar results of 99. 9999% or higher were obtained except for Example 2. Even in Example 2, the effect was as high as 99.99%.
- the mask of the present invention configured to include filter members having a virus inactivating ability can inactivate viruses once adhering to the mask in about 1 hour, which varies depending on the amount of the virus inactivating fine particles and the like. Therefore, the mask provided is not a single use mask and can be used for a long time.
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Claims (6)
- Eine Maske, die in der Lage ist, ein daran haftendes Virus zu inaktivieren, wobei die Maske dadurch gekennzeichnet ist, dass diese umfasst:einen Maskenkörper, der mit einem Element versehen ist, welches verwendet wird, wenn die Maske getragen wird; undvirusinaktivierende feine Teilchen, die die Fähigkeit haben, Viren zu inaktivieren und von dem Maskenkörper gehalten werden, wobei die virusinaktivierenden feinen Teilchen Teilchen aus mindestens einem, ausgewählt aus der Gruppe bestehend aus Platin(II)-Iodid, Palladium(II)-Iodid, Silber(I)-Iodid, Kupfer(I)-Iodid und Kupfer(I)-Thiocyanat, sind;wobei die virusinaktivierenden feinen Teilchen an dem Maskenkörper mindestens durch ein Silanmonomer und/oder ein Polymerisationsprodukt des Silanmonomers befestigt sind.
- Eine Maske, die in der Lage ist, ein daran haftendes Virus zu inaktivieren, wobei die Maske dadurch gekennzeichnet ist, dass diese umfasst:einen Maskenkörper, der mit einem Element versehen ist, welches verwendet wird, wenn die Maske getragen wird; undvirusinaktivierende feine Teilchen, die die Fähigkeit haben, Viren zu inaktivieren und von dem Maskenkörper gehalten werden, wobei die virusinaktivierenden feinen Teilchen Teilchen aus mindestens einem, ausgewählt aus der Gruppe bestehend aus Platin(II)-Iodid, Palladium(II)-Iodid, Silber(I)-Iodid, Kupfer(I)-Iodid und Kupfer(I)-Thiocyanat, sind;wobei die virusinaktivierenden feinen Teilchen von dem Maskenkörper durch Gruppen von anderen anorganischen feinen Teilchen gehalten werden, die an dem Maskenkörper durch chemische Bindungen mit einem Silanmonomer und/oder einem Polymerisationsprodukt des Silanmonomers befestigt sind.
- Die Maske nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Maskenkörper eine Vielzahl von atmungsaktiven Filterelementen enthält, die in einer Dickerichtung des Maskenkörpers aufgeschichtet sind und die virusinaktivierenden feinen Teilchen von mindestens einem der Vielzahl von Filterlementen, aus denen der Maskenkörper besteht, gehalten werden.
- Die Maske nach Anspruch 3, dadurch gekennzeichnet, dass die virusinaktivierenden feinen Teilchen von mindestens einem Filterelement gehalten werden, das sich auf der innersten Seite befindet, wenn die Maske getragen wird.
- Die Maske nach Anspruch 3 oder 4, dadurch gekennzeichnet, dass die virusinaktivierenden feinen Teilchen von mindestens einem Filterelement gehalten werden, das sich auf der äußersten Seite befindet, wenn die Maske getragen wird.
- Die Maske nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass ein durchschnittlicher Durchmesser der virusinaktivierenden feinen Teilchen 1 nm oder größer und kleiner als 500 nm ist.
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JP2009228884 | 2009-09-30 | ||
PCT/JP2010/005894 WO2011040035A1 (ja) | 2009-09-30 | 2010-09-30 | マスク |
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EP2484409A4 EP2484409A4 (de) | 2016-04-27 |
EP2484409B1 true EP2484409B1 (de) | 2018-02-14 |
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EP (1) | EP2484409B1 (de) |
JP (1) | JP5291198B2 (de) |
KR (1) | KR101772716B1 (de) |
CN (1) | CN102548619A (de) |
AU (1) | AU2010302079B2 (de) |
BR (1) | BR112012006914B1 (de) |
CA (1) | CA2776031C (de) |
IN (1) | IN2012DN02357A (de) |
RU (1) | RU2549065C2 (de) |
WO (1) | WO2011040035A1 (de) |
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CN102548619A (zh) | 2012-07-04 |
IN2012DN02357A (de) | 2015-08-21 |
JP5291198B2 (ja) | 2013-09-18 |
AU2010302079A1 (en) | 2012-04-12 |
RU2549065C2 (ru) | 2015-04-20 |
EP2484409A4 (de) | 2016-04-27 |
WO2011040035A1 (ja) | 2011-04-07 |
CA2776031C (en) | 2018-09-18 |
RU2012115650A (ru) | 2013-11-10 |
BR112012006914A2 (pt) | 2020-10-06 |
EP2484409A1 (de) | 2012-08-08 |
US10744351B2 (en) | 2020-08-18 |
BR112012006914B1 (pt) | 2021-06-01 |
KR20120096477A (ko) | 2012-08-30 |
KR101772716B1 (ko) | 2017-08-29 |
US20120192876A1 (en) | 2012-08-02 |
JPWO2011040035A1 (ja) | 2013-02-21 |
AU2010302079B2 (en) | 2015-04-02 |
CA2776031A1 (en) | 2011-04-07 |
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